EP2774194B1 - Procede de fabrication d'electrodes de batteries entierement solides - Google Patents

Procede de fabrication d'electrodes de batteries entierement solides Download PDF

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EP2774194B1
EP2774194B1 EP12794400.7A EP12794400A EP2774194B1 EP 2774194 B1 EP2774194 B1 EP 2774194B1 EP 12794400 A EP12794400 A EP 12794400A EP 2774194 B1 EP2774194 B1 EP 2774194B1
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particles
electrode
materials
previous
substrate
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EP2774194A1 (fr
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Frédéric BOUYER
Bruno Vuillemin
Fabien Gaben
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I Ten SA
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
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    • H01M4/0402—Methods of deposition of the material
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    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
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    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/045—Electrochemical coating; Electrochemical impregnation
    • H01M4/0457—Electrochemical coating; Electrochemical impregnation from dispersions or suspensions; Electrophoresis
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    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
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    • H01M4/043—Processes of manufacture in general involving compressing or compaction
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    • H01M4/00—Electrodes
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    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H01M4/0435—Rolling or calendering
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention belongs to the field of batteries and in particular lithium ion batteries. It relates more particularly to fully solid lithium ion battery electrodes, and a novel method of manufacturing such battery electrodes.
  • the ideal battery for powering standalone electric devices such as: phone and laptops, portable tools, autonomous sensors
  • traction of electric vehicles would have a long life, would be able to store both large amounts of energy and power, and would not present a risk of overheating or even explosion.
  • Li-ion batteries lithium ion batteries
  • Li-ion batteries have the best energy density among the various storage technologies proposed.
  • electrodes for making Li-ion batteries there are different architectures and chemical compositions of electrodes for making Li-ion batteries.
  • Li-ion batteries The methods of manufacturing Li-ion batteries are presented in numerous articles and patents, and the book “Advances in Lithium-Ion Batteries” (W. van Schalkwijk and B. Scrosati), published in 2002 (Kluever Academic / Plenum Publishers ) gives a good inventory.
  • the electrodes of Li-ion batteries can be manufactured using coating techniques (including: roll coating, doctor blade, tape casting). With these processes, the active materials used to make the electrodes are in the form of powders whose average particle size is between 5 and 15 microns in diameter. These particles are embedded in an ink which consists of these particles and deposited on the surface of a substrate.
  • the inks (or pastes) deposited to form the electrodes contain particles of active materials, but also binders (organic), carbon powder to ensure electrical contact between the particles, and solvents that are evaporated during the step of drying the electrodes.
  • a calendering step is performed on the electrodes. After this compression step, the active particles of the electrodes occupy about 60% of the volume of the deposit, which means that there is generally 40% of porosities between the particles.
  • the contact between each of the particles is essentially punctual and the structure of the electrode is porous.
  • the porosities are filled with an electrolyte, which may be liquid (aprotic solvent in which a lithium salt is dissolved) or in the form of a more or less polymerized gel impregnated with a lithium salt. Since the thicknesses of the li-ion battery electrodes are generally between 50 and 400 ⁇ m, the lithium ions are transported in the thickness of the electrode via the pores which are filled with electrolyte (containing lithium salts). . Depending on the amount and size of the porosities, the diffusion rate of lithium in the thickness of the electrode varies.
  • the lithium ions must diffuse both in the thickness of the particle and in the thickness of the electrode (ie the coating).
  • the diffusion in the particle of active material is slower than in the electrolyte.
  • the particle size must be reduced, and in standard li-ion batteries it is between 5 and 15 microns.
  • the powers and energies of the battery can be modulated depending on the thickness of the deposits, the sizes and density of active particles contained in the ink, the powers and energies of the battery can be modulated.
  • the increase in energy densities is necessarily at the expense of the power density.
  • the high power battery cells require the use of electrodes and separators of small thickness and very porous, while the increase in energy density requires instead to increase these same thicknesses and reduce the porosity rate.
  • the article " "Optimization of Porosity and Thickness of a Battery Electrode by Means of a Reaction-Zone Model” by John Newman, J. Electrochem, Soc., Vol 142, No.1, January 1995 demonstrates the respective effects of electrode thicknesses and their porosity on their discharge regime (power) and energy density.
  • the porosities of the electrodes must be filled with electrolyte. This filling is only possible if the porosities are open. In addition, depending on the size of the pores, their tortuosity, the impregnation of the electrode with the electrolyte can become very difficult, if not impossible.
  • the porosity rate, impregnated with electrolyte decreases, the electrical resistance of the deposit decreases and its ion resistance increases. When the porosity falls below 30% or even 20%, the ionic resistance increases sharply because some porosities are then likely to close, which prevents wetting of the electrode by the electrolyte.
  • the thickness of these films is appropriate to limit the thickness of these films to less than 20 microns, and preferably less than 10 microns. , to allow fast diffusion of lithium ions in the solid, without loss of power.
  • the current deposition techniques described above do not allow to precisely control the deposit thickness.
  • the dry extracts used and the viscosities of the associated inks do not make it possible to go below 20 ⁇ m in thickness.
  • Such totally inorganic films confer excellent performance in aging, safety and temperature resistance.
  • PVD deposition is the most widely used technology for the manufacture of thin film microbatteries. Indeed, these applications require films free of porosity and other point defects to ensure a low electrical resistivity, and the good ionic conduction necessary for the proper functioning of the devices.
  • the deposition rate obtained with such technologies is of the order of 0.1 ⁇ m to 1 ⁇ m per hour.
  • PVD deposition techniques make it possible to obtain deposits of very good quality, containing virtually no point defects, and allow deposits to be made at relatively low temperatures.
  • This technique is perfectly adapted to the production of thin layers, but as soon as we try to increase the thickness of the deposit (for example thicknesses greater than 5 ⁇ m), columnar growths appear, and the time of deposit becomes too important to consider an industrial use in the field of microbatteries in thin layers.
  • Patent applications US 2007/184345 , WO 2007/061928 , US 2008/286651 and WO 2010/011569 describe electrochemical devices comprising a cathode deposited by techniques other than vacuum deposition; they describe in particular the deposition of a cathodic layer by electrophoresis from a micron size powder of LiCoO 2 ; this layer however has cavities, and it must be densified by sintering at high temperature, close to the melting temperature of the deposited material. The other parts of the battery are obtained by vacuum deposition.
  • the patent US 7,790,967 (3G Solar Ltd) also describes the deposition of a nanoporous TiO 2 electrode by electrophoresis from a suspension of TiO 2 nanoparticles;
  • the thickness of the electrode is of the order of 10 microns.
  • the patent JP 4501247 discloses a method of manufacturing an electrode for a battery in which a layer of an active material is formed by electrophoresis. More Specifically, this patent describes a method in which a charge collector is immersed in a solution comprising an active material in a solvent, this process being part of a more general method of manufacturing a battery electrode. The electrophoresis of said active material contained in the solution is carried out by generating an electrical potential gradient in this solution, the active material forming a layer of active material on the surface of the collector, and adhering to said collector surface.
  • the manufacture of cathodes for Li-ion batteries by this method is mentioned. The techniques used to make the anode and the electrolyte are not indicated. The cathodes obtained in this patent are porous.
  • a first object of the invention is to provide electrode layers (anode and / or cathode) for Li-ion battery, with few defects.
  • Another object of the invention is to manufacture electrode layers for Li-ion battery industrially, on a large scale, and on large areas at lower cost.
  • Another object of the invention is to produce layers of high geometric precision, with a very small amount of defects and with high deposition rates, which can be used for producing electrode films for batteries.
  • melting temperature here includes the decomposition temperature for substances that do not have a melting point.
  • the electrode manufacturing method further comprises a step of mechanical compaction (typically by compression) of the dried layer, carried out before or simultaneously with the thermal densification step.
  • a step of mechanical compaction typically by compression
  • the mechanical compaction step is carried out by applying a compression pressure of between 20 and 100 MPa, and preferably between 40 and 60 MPa. In some embodiments, however, the pressure applied is greater than 250 MPa, or even greater than 400 MPa.
  • the step of thermal densification and / or mechanical compaction is carried out under vacuum, in order to avoid the oxidation of the metal substrate.
  • Said substrate may be a conductive substrate.
  • the average size D 50 of the particles of electrode material is less than 100 nm and more preferably less than or equal to 30 nm.
  • Said electrode may be an anode or a cathode.
  • the deposited electrode layer has a thickness of less than 20 ⁇ m, preferably less than approximately 10 ⁇ m, and even more preferentially less than 5 ⁇ m.
  • electrically conductive nanoparticles may be deposited together with the electrode materials.
  • nanoparticles of conductive materials of lithium ions in another embodiment, more fusible than the electrode particles can be deposited simultaneously with the particles of electrode material. This more fusible material will bind the particles together, thus ensuring the continuity of the diffusion path of lithium ions.
  • the electrode is entirely solid and the porosities between the active particles are filled by this fusible phase.
  • lithium salts can be LiCl, LiBr, LiI, Li (ClO 4 ), Li (BF 4 ), Li (PF 6 ), Li (AsF 6 ), Li (CH 3 CO 2 ), Li (CF 3 SO 3 ), Li (CF 3 SO 2 ) 2 N, Li (CF 3 SO 2 ) 3 , Li (CF 3 CO 2 ), Li (B (C 6 H 5 ) 4 ), Li (SCN), Li (NO 3 ).
  • the nanoparticles of polymer may be polyimides, PVDF, PEO (polyethylene oxide), polymethacrylates, polysiloxanes.
  • the zeta potential of the electrode material particle suspensions is greater than 40 mV, and preferably greater than 60 mV. Such suspensions are very stable and contain few agglomerates of particles, thereby allowing deposits with few defects.
  • the suspensions of electrode material particles further contain a steric or preferably electrostatic stabilizer. This stabilizer makes it possible to further improve the stability of the suspension, and consequently the quality of the deposited film.
  • the electrode material suspensions do not contain stabilizer.
  • the suspensions without stable stabilizers advantageously have dry extracts of between 2 and 20 g / l, the size of the particles being preferably less than 100 nm, and even more preferably less than 50 nm.
  • the Zeta potential of the suspension is generally less than 40 mV, and more particularly between 25 and 40 mV.
  • Another object of the invention is the use of the method in the manufacture of batteries, in particular lithium ion type batteries, which are entirely solid.
  • Yet another object is an electrode layer in a fully solid battery, obtainable by the process described above, characterized in that it comprises at least one phase consisting of anode or cathode active materials, and minus one conductive phase of the lithium ions and / or electronic conductor, said phases being crystallized with a grain size of between 1 and 100 nm.
  • the term "electrophoretic deposition” or “electrophoretic deposition” means a layer deposited by a method of depositing electrically charged particles on the surface, previously suspended in a liquid medium, on a substrate, the displacement of the particles towards the surface of the substrate being generated by the application of an electric field between two electrodes placed in the suspension, one of the electrodes constituting the conductive substrate on which the deposit is made, the other electrode (“counter-electrode”) being laid in the phase liquid.
  • a compact deposition of particles is formed on the substrate, if the zeta potential has an appropriate value as will be explained below.
  • the size of a particle is its largest dimension.
  • a “nanoparticle” is a particle of which at least one of the dimensions is less than 100 nm.
  • the “particle size” or “average particle size” of a powder or set of particles is given in D 50 .
  • the "zeta potential" of a suspension is defined as the potential difference between the breast of the solution and the shear plane of the particle. It is representative of the stability of a suspension.
  • the shear plane (or hydrodynamic radius) corresponds to an imaginary sphere around the particle in which the solvent moves with the particle as the particles move in the solution.
  • the theoretical basis and the determination of the zeta potential are known to the electrochemist who develops deposits by electrophoresis; it can be deduced from the electrophoretic mobility.
  • This equipment measures, using optical devices, the particle displacement velocities as a function of the electric field applied to them. Also, it is necessary that the solution is very diluted to allow the passage of the light.
  • acoustophoresis techniques for example using a device called "acoustosizer” from Colloidal Dynamics. The velocity of the particles is then measured by acoustic techniques.
  • dispenser means a compound capable of stabilizing the colloidal suspension and in particular to prevent the particles from agglomerating.
  • “Sintering” is understood to mean a process making a system consisting of individual particles (or a porous agglomerate) by heat treatment, in the absence of external pressure exerted or under the effect of such pressure, so that least some of the properties of the system (if not all) are modified in the direction of a reduction of the overall free energy of the system. At the same time, this evolution leads to a significant (if not complete) decrease in the initial porosity. Finally, the process assumes that at least one solid phase exists constantly throughout the heat treatment, so as to maintain a certain stability of shape and dimension to the considered system.
  • the method according to the invention comprises the essential step of electrophoretic deposition of particles of cathode materials and / or anode.
  • Such a method makes it possible to significantly reduce the amount of defects in the layers obtained compared with known processes, in particular large porosities, cavities, cracks and agglomerates; the quality of the deposited layers is better when the suspension from which the deposit is made is sufficiently stable.
  • the method according to the invention allows the deposition of electrode layers. These layers have a thickness generally less than about 20 microns, preferably less than about 10 microns, and even more preferably less than 5 microns.
  • the process for manufacturing fully solid thin-film batteries according to the present invention has an advantageous alternative to known techniques, and particularly to PVD deposition techniques, by making it possible to make very dense deposits, at low temperature, over large areas of substrate. , with high deposition rates, easily controllable thicknesses and very accurately (depending on the size of the particles), over a wide range of thickness ranging from one tenth of a micron to several tens or even hundreds of microns, without inducing very expensive investments in complex and unproductive machines.
  • FIGS. 1a to 1c illustrate the differences between the porosities 3 intra-agglomerates, located between the particles 2 , and that we will call in this document "porosities", and the pores 6 inter-agglomerates, located between the agglomerates 5 and that we will call “cavities” 6 .
  • the deposit is preferably made from SP + or SP- very colloidal suspensions. stable.
  • the stability of the suspensions depends on the size of the particles P +, P-, as well as the nature of the solvent used and the stabilizer used to stabilize the colloidal suspension.
  • SP + is meant a colloidal suspension containing particles " P +” of materials making it possible to obtain a cathode film
  • SP - a colloidal suspension containing particles P - of materials making it possible to obtain a film of 'anode.
  • colloidal suspensions containing particles of nanometric size are preferred. These particles preferably have an average particle size D 50 of less than 100 nm, and more preferably (especially in the case where the suspension comprises particles of high melting point materials) less than 30 nm. In fact, with particles of small dimensions, the densification of the deposit is greatly facilitated since the deposit is compact.
  • the stability of the suspensions can be expressed by their zeta potential.
  • the suspension is considered stable when its zeta potential is greater than 40 mV, and very stable when it is greater than 60 mV.
  • the zeta potential is less than 20 mV, agglomerates of particles can appear.
  • the deposits are in certain embodiments made from colloidal suspensions having a zeta potential greater than 40 mV, and even more preferably 60 mV (in absolute value).
  • the suspensions have low particulate solids and the Zeta potential is less than 40 mV as described in more detail below.
  • the colloidal suspensions for use in electrophoresis comprise an electrical insulating solvent, which may be an organic solvent, or deionized water, or a mixture of solvents, and particles to be deposited; the colloidal suspensions may also comprise one or more stabilizers.
  • an electrical insulating solvent which may be an organic solvent, or deionized water, or a mixture of solvents, and particles to be deposited; the colloidal suspensions may also comprise one or more stabilizers.
  • the particles do not agglomerate together to create clusters capable of inducing cavities, agglomerates and / or significant defects in the deposit.
  • the particles remain isolated in the suspension.
  • the stability of the slurry required to obtain a compact deposit is achieved through the addition of stabilizers.
  • the stabilizer prevents flocculation of the powders and the formation of agglomerates. It can act by an electrostatic effect or by a steric effect. Electrostatic stabilization is based on the electrostatic interactions between charges and is obtained by the distribution of charged species (ions) in the solution. Electrostatic stabilization is controlled by the surface charge of the particles; it can therefore depend on the pH. Steric stabilization uses polymers, nonionic surfactants or even proteins, which, added to the suspension, are absorbed on the surface of the particles to cause repulsion by congestion of the inter-particle space. A combination of both stabilization mechanisms is also possible. In the context of the present invention, electrostatic stabilization is preferred which is easy to implement, reversible, inexpensive, and which facilitates the subsequent consolidation processes.
  • the particles and / or agglomerates preferably have a size of less than 100 nm, and more preferably less than 50 nm.
  • suspensions were obtained for low solids, ranging between 2 g / l and 20 g / l, preferably between 3 and 10 g / l, and more particularly for dry extracts of the order of 4 g / l, in an organic solvent of the alcohol and / or ketone type.
  • These stable colloidal suspensions of particles without addition of stabilizer are particularly preferred in the context of the present invention.
  • the Zeta potential of such suspensions is generally less than 40 mV, and more particularly between 25 and 40 mV. This could mean that such suspensions tend to be unstable, however the inventors have found that the use of these suspensions for electrophoretic deposition led to very good quality deposited films.
  • deposition voltages of less than 5 V should be preferred. Indeed, above 5 V the water is likely to undergo electrolysis giving rise to gas production on the electrodes that make the porous deposits and reduce their adhesion to the substrate. In addition, galvanic reactions in an aqueous medium give rise to the formation of metal cations that can pollute the deposits.
  • the deposits are in the solvent phase. It is thus possible to work at higher voltage values, thus increasing the rates of deposition.
  • nanoparticles of electronically conductive materials may be added to the materials mentioned above.
  • some electrode materials are poor ionic and electrical conductors, therefore when the thicknesses deposited are greater than 0.5 microns the electrode may be too resistive, and it no longer works.
  • thicknesses of 1 to 10 microns are generally desirable for the electrodes, in order to have batteries with good energy densities. In this case it is necessary to co-depositing particles of electrode materials and conductive particles (ionic and / or electrical).
  • the lithium salts can be LiCl, LiBr, LiI, Li (ClO 4 ), Li (BF 4 ), Li (PF 6 ), Li (AsF 6 ), Li (CH 3 CO 2 ), Li (CF 3 SO 3 ), Li (CF 3 SO 2 ) 2 N, Li (CF 3 SO 2 ) 3 , Li (CF 3 CO 2 ), Li (B (C 6 H 5 ) 4 ), Li (SCN), Li (NO 3 ).
  • the polymers may be polyimides, PVDF, PEO (polyethylene oxide), polymethacrylates, polysiloxanes.
  • the nanoparticles are suspended in a suitable liquid phase.
  • a stabilizer is added to obtain a suspension whose zeta potential is preferably greater than 40 mV, and more preferably greater than 60 mV.
  • suspensions containing no stabilizers and in particular suspensions having low solids (generally less than 20 g / l), and in particular suspensions containing particles smaller than 100 nm, are used, and preferably less than 50 nm.
  • the Zeta potential of the suspension is generally between 25 and 40 mV.
  • the solvents used may be based on ketone, alcohol or a mixture of both.
  • PEI polyethyleneimine
  • PAA polyacrylic acid
  • citric acid nitrocellulose provided that they are soluble in the chosen organic solvent.
  • Electrostatic stabilizations can be achieved by adding iodide, adding acids or bases.
  • the acidification or basification of the solution can be carried out by adding traces of water and acids when the suspension is carried out in the solvent phase.
  • the electrical conductivity of the suspension can be controlled to obtain a significant potential gradient between the two electrodes, without risk of dielectric breakdown.
  • the conductivity of the colloidal suspension is between 1 and 20 ⁇ S / cm. Strong acids and bases can be added in small amounts to control the conductivity of the suspension and charge the surfaces of the particles.
  • the defects created in the particles during the grinding dispersion stages are also likely to reduce the densification temperature, as well as the realization of mechanical compressions.
  • the electrode layer is deposited electrophoretically.
  • the electrophoretic deposition of particles is done by the application of an electric field between the substrate on which the deposit is made and a counter electrode, to put the charged particles of the colloidal suspension in motion, and to deposit them on the substrate.
  • the absence of binders and other solvents deposited on the surface with the particles makes it possible to obtain very compact deposits.
  • the compactness obtained thanks to the electrophoretic deposition, and the absence of organic compounds in large quantity in the deposit makes it possible to limit or even avoid the risk of cracks or the appearance of other defects in the deposit during the drying steps.
  • the process according to the present invention does not require steps of burning or evaporation of corrosive or harmful compounds. .
  • the increase in economic and environmental constraints makes it necessary to reduce discharges into the atmosphere, so the present invention responds well to these constraints.
  • the deposition rate can be very high depending on the applied electric field and the electrophoretic mobility of the particles of the suspension.
  • deposition rates of the order of 10 ⁇ m / min can be obtained.
  • the figure 9 illustrates the operating principle of electrophoretic deposits.
  • the inventor has found that this technique makes it possible to deposit on very large surfaces with excellent homogeneity (provided that the concentrations of particles and electric fields are homogeneous on the surface of the substrate). It is equally suitable for a continuous strip process, that is to say the substrate is advantageously a strip; during the electrophoretic deposition, the band is advantageously stationary relative to the liquid phase.
  • the substrate may be a sheet or a strip having a conductive surface.
  • a copper or aluminum strip of a thickness which may be for example 6 ⁇ m may be used, or a polymer strip having an electrically conductive surface deposit.
  • the substrate is a thin sheet of aluminum.
  • aluminum substrates are compatible with anaphoretic deposition processes, unlike some other metals and in particular copper which tends to dissolve into anodic polarization. This surface dissolution of the copper strips does not make it possible to create a stable anchoring base for the electrode deposits.
  • the inventors have noticed that with the nanoparticles of the battery materials, it was possible to obtain colloidal suspensions of particles, without adding stabilizers, but that these nanoparticles were still negatively charged and therefore compatible with anaphoresis deposits.
  • each of the cathode and anode layers is preferably between 5 ⁇ m and 20 ⁇ m.
  • Electrophoresis deposition can be carried out in a batch process (static) or in a continuous process.
  • the Figures 8a and 8b illustrate different embodiments of electrophoretic deposits, for producing both thin strips or coatings on conductive substrate.
  • a stabilized power supply makes it possible to apply a voltage between the conductive substrate and two electrodes located on either side of this substrate.
  • This voltage can be continuous or alternative.
  • Accurate tracking of the currents obtained makes it possible to accurately monitor and control the thicknesses deposited.
  • the deposited layers are insulating, depending on their thickness, they can affect the value of the electric field, so in this case, a controlled current deposition mode is preferred.
  • the value of the electric field is changed.
  • the figure 8a shows schematically an installation for implementing the method according to the invention.
  • the power supply located between the counterelectrodes 43 and the conductive substrate 44 is not shown.
  • An electric field is applied between the two counter electrodes 43 and the substrate 44 to deposit particles of the colloidal suspension 42 on both sides of the substrate 44 .
  • the electrically conductive strap (strip) 44 serving as substrate is unwound from an unwinder 41 .
  • the deposited layer is dried in a drying oven 45 and consolidated by mechanical compaction using a suitable compaction means 46 .
  • the compaction can be performed under a controlled atmosphere and for temperatures between room temperature and the melting temperature of the deposited materials.
  • figure 8a is useful for the manufacture of active material deposits on current collectors for producing battery electrodes. However, it can be limited to coating only one side of the substrate. Also, figure 8b represents a device for producing a coating on a single conductive surface, without mechanical compaction.
  • this deposition technique allows a perfect recovery of the surface whatever its geometry, the presence of roughness defects.
  • any less well-coated zones are more conductive and thus locally concentrate a higher deposition rate which tends to compensate for or erase the defect.
  • the deposits obtained are thus inherently of excellent quality, with few defects and very homogeneous.
  • the densification temperature it is preferred not to exceed 600 ° C, more preferably not more than 500 ° C. In some embodiments, the temperature is between 180 ° C and 400 ° C.
  • Densification at such temperatures requires that the film obtained after the deposition is compact, that is to say without meso porosities (cracks, cavities), aggregates. This is enabled by the electrophoresis deposition method as described above.
  • the deposited particles are of nanometric sizes as described above, and preferably less than 50 nm in size, more preferably less than 30 nm.
  • the heat treatment temperature also depends on the application or not of a pressure, the pressure can be applied before, after or during the heat treatment. When pressure is applied, the heat treatment temperature can be lowered.
  • the pressure applied is advantageously between 20 and 100 MPa.
  • the applied pressure is greater than 250 MPa, or even greater than 400 MPa.
  • the substrate of the electrode layers is preferably composed of a generally metallic electrical conductive material.
  • the substrate is metallic, it is preferred to avoid heating it to high temperatures during the manufacture of the battery, in order to avoid any risk of oxidation and deterioration of the surface properties.
  • the reduction of the surface oxidation is particularly beneficial for reducing electrical contact resistances, essential point to the operation of storage devices and / or energy production.
  • electrophoretic layers of very good quality as described above, and in particular of compact layers makes it possible to reduce the duration and the temperature of the heat treatments and to limit the shrinkage of these treatments, and to obtain a structure homogeneous nanocrystalline This contributes to obtaining dense layers without defects.
  • the inventor has found that the smaller the size of the deposited particles, the lower the temperature of the heat treatment can be. It is thus possible to produce deposits in thin layers, or relatively thick, with porosity levels of less than 5% or even 2% without resorting to temperatures and / or significant heat treatment times. In addition, this low-temperature deposit compaction technology significantly reduces the risk of shrinkage. Also, it is no longer necessary to use very complex and expensive heat treatment cycles to consolidate the ceramic deposits of battery electrode films.
  • phase (s) of thermal densification and / or mechanical compaction it may be advantageous to work under vacuum, or under an inert atmosphere to avoid the appearance of pollution on the surfaces of the particles that could harm the densification mechanism particles between them.
  • Densifying the deposition may thus be carried out at temperatures below 0.7 T f, preferably 0.5T f or 0,3T f wherein T f is the melting point (in ° C) the solid material of chemical composition identical to that of the deposited particle.
  • T f is the melting point (in ° C) the solid material of chemical composition identical to that of the deposited particle.
  • the heat treatment temperature is chosen with respect to the melting temperature of the most fuse material, ie having the lowest melting temperature .
  • Such a method of manufacturing electrode layers can be used directly on substrates such as aluminum strips having low melting temperatures.
  • Nanoparticles being very sensitive to surface pollution, it is however preferable to carry out consolidation treatments under vacuum, or in an inert atmosphere.
  • the method according to the invention can be used in the manufacture of a Li-ion battery.
  • steps 1.A and 1.B a cathode and anode film is deposited by electrophoresis, respectively, on a conductive substrate. This deposit can be performed on both sides of the conductive substrate.
  • Steps 2.A and 2.B the film deposited by electrophoresis.
  • steps 3.A and 3.B it is densified by mechanical and / or thermal means. This densification makes it possible to obtain a density greater than 90% of the theoretical density of the solid body, or even greater than 95%.
  • the electrolyte film is deposited on the anode and on the cathode, respectively, by any appropriate means.
  • the thickness of the deposited film may be of the order of 1 ⁇ m.
  • this deposit also covers the edges (i.e. the slices) of the electrodes. This isolation of the edges of the electrodes avoids both the risk of short circuit and the risk of leakage currents.
  • this electrolyte deposit is dried.
  • an edge of the electrodes is cut.
  • the edge bound to the strip is cut in order to leave three edges coated with electrolyte on the wafer. Since this electrolyte is a dielectric, during the next stacking step, it will only reveal the anode contacts on one side of the cell, respectively cathodic on the other, in order to make parallel connections of the battery cells. to form a battery cell with higher capacity.
  • step 7 the stack is made so that on two opposite sides of the stack is alternately a succession of cut anode edges and cathode edges coated with electrolyte.
  • this stack can be densified to obtain a good bond ("solder") between the two faces of the electrolyte layer.
  • the melting temperature of the anode and cathode layers is significantly greater than that of the electrolyte layer, it is preferable to perform the thermal densification of the anode and cathode layers separately, before stacking, and then thermal densification of the stack to densify the electrolyte layer.
  • terminations are added at the level where the cathodic current collectors, respectively anodic, are apparent (not coated with insulating electrolyte). These contact areas may be on opposite sides of the stack to collect current, but also on the same sides or on adjacent sides.
  • the stack is made by winding two half-electrodes together on a mandrel in order to obtain a cylindrical cell.
  • the anode connections then leave on one side, while the cathode connections leave the other side.
  • FIGS. 2a to 2b ' illustrate the different steps of a deposition of an electrode layer by electrophoresis according to the invention.
  • the figure 2a represents the supply of a substrate, here in the form of a metal strip 1 .
  • the Figure 2a ' represents the supply of a substrate, here in the form of a metal strip 1 , in this step a partial protection of the surface of the substrate 1 with the aid of an insulating mask 9 is produced.
  • This mask may be a strippable polymer film.
  • the Figures 2b and 2b ' represent the electrophoretic deposition of the cathode nanoparticles 24 on the conductive parts of the substrate 1 .
  • the deposit is made over the entire surface, and on both sides, of the substrate 1 , while on the figure 2b ' part of the substrate is protected by the insulating mask 9 .
  • the product obtained by the process according to Figures 2a to 2b ' corresponds to the case where the substrate is supplied in the form of a band.
  • FIGS. 3a to 3b ' represent identical products to those of Figures 2a to 2b ' except that the cathode layer additionally covers a wafer of the substrate.
  • the metal substrate strip can be replaced by a metallized polymer film, the film being "strippable", i.e., it can be dissolved in a suitable solution, or peelable.
  • the figure 4a represents the supply of a substrate 60 , here in the form of a "strippable" polymer film 61 coated with a metal layer 62 ,
  • the figure 4b represents the electrophoretic deposition of the cathode nanoparticles 63 on the conductive portions of the substrate 60 .
  • the figure 4c represents the stripping (or peeling) of the polymer film.
  • the figure 4d represents the deposition of the cathode nanoparticles 63 on the metal layer 62 exposed in the step of the figure 4c .
  • the figure 5a represents the supply of a substrate 70 , here in the form of a metal film 62 coated on both sides with a photosensitive polymer resin film 61a , 61b.
  • the figure 5b represents the savings made with the polymer 61a partially insolated and developed on one of the faces of the metal film 62 , with realization of a savings 64a.
  • the figure 5c represents the electrophoresis deposition of the cathode nanoparticles 63 on the conductive portions of the substrate 60 (part not covered with polymer or photoresist).
  • the figure 5d represents the savings made with the polymer 61b partially insolated and developed on the other side of the metal film 62 , with realization of a savings 64b .
  • the figure 5e represents the electrophoretic deposition of the cathode nanoparticles 63 on the conductive portions of the substrate 60 (part of the metal film 62 not covered with a polymer or photoresist or with cathode particles 63 ).
  • the figure 5f represents the stripping of savings 64a, 64b.
  • the figure 6a represents the supply of a substrate, here in the form of an insulating plate 65 partially coated with metal films 68a, 68b corresponding to step d) of the main embodiment of the invention.
  • the figure 6b represents the electrophoretic deposition of the cathode nanoparticles 63 on the metal part of the substrate 68a.
  • the Figure 6c represents the deposition of an electrolyte film 66 on the metallic part of the substrate 68a covered with cathode 63 .
  • the figure 6d represents a sectional view of the battery after deposition of the anode thin film.
  • the figure 10 represents the compact deposition of nanoparticles of non-homogeneous sizes 2 , 17.
  • Such a stack can be obtained directly by co-depositing a mixture of nanoparticles of different sizes or by successive deposition of particles of different sizes.
  • the figure 12a represents the diffusion path of lithium in a compact stack of particles impregnated with electrolyte. There is a surface contact area 76 between the particles and the electrolyte contained in the porosities. The path of diffusion little resistive. There is also a point contact zone 77 between the particles. The diffusion of lithium on this point contact is limited.
  • the figure 12b represents the evolution of the interface between the particles during consolidation.
  • the diffusion path 78 can be provided in the solid phase, without the use of a liquid electrolyte in the pores
  • the figure 12c represents the structure obtained after densification of a composite deposit containing a "fuse" phase 79 .
  • the figure 12d shows schematically the influence of densification on the type of porosity. This point can justify that our batteries have porosities lower than 30%. At this level, they are closed and can no longer be impregnated with electrolyte.
  • spinel LiMn 2 O 4
  • the electrodes that can be obtained by the process according to the invention are distinguished from the known electrodes by a number of structural features.
  • the electrode is preferably entirely solid, and may have a composition that can not be obtained by vacuum deposition.
  • the degree of porosity of the anode and / or cathode layers expressed as the difference between the theoretical density of the layers and the actual density / theoretical density of the layers, is low and can be less than 10% or even 5%, whereas the known processes lead to a porosity rate which remains generally greater than 20%.
  • the size of the grains can be much smaller than in thin-film batteries deposited by inks, because the layer deposited by electrophoresis is denser, even before densification.
  • the electrode is composed solely of inorganic materials which contain neither lithium salts nor impregnated ionic liquids, which makes it possible to avoid the problems of corrosion on the current collectors, which can then be both aluminum compounds, less expensive than copper or silver.
  • the use of aluminum is often not possible or limited to the cathode, either because their manufacture involves temperatures that are too high compared to the melting point of aluminum or because an aluminum collector could be corroded by the lithium salts in the electrolytes and by the extreme voltages to which the collectors in the batteries are subjected.
  • the fact of using within the same battery only one material for the collectors facilitates their recycling.
  • the invention has many advantages.
  • the method of manufacturing the anode and cathode layers by electrophoresis is simple, fast, inexpensive.
  • the electrode layer does not contain organic materials or lithium salts.
  • the process according to the invention does not need to be carried out in a dry atmosphere, unlike the processes according to the state of the art using highly sensitive lithium or lithium metal salts. to moisture.
  • the absence of corrosive lithium salts improves the life of the battery, decreases the risk of internal short circuit and also improves its resistance to temperature; as a result, the batteries comprising an electrode layer deposited by the process according to the invention can undergo a wave soldering operation, unlike known thin-film lithium ion batteries.
  • the batteries according to the invention have a better level of security.
  • a LiMn 2 O 4 powder consisting of nanoparticle clusters is synthesized.
  • the method of Pechini described in the article Synthesis and Electrochemical Studies of Spinel Phase LiMn2O4 Cathode Materials Prepared by the Pechini Process, W. Liu, GC Farrington, F. Chaput, B. Dunn, J. Electrochem. Soc., Vol.143, No.3, 1996
  • the powder contains clusters whose size is between 50 nm and 100 nm.
  • This powder is then suspended in ethanol with a concentration of 20 g / l.
  • the SP + suspension is introduced into the bowl of a ball mill previously filled with ceramic balls of diameter 0.1 mm. Grinding for 2 hours in the presence of polyacrylic acid as a complexing agent, which allows to obtain a colloidal solution having particles (D 50 ) whose size is equal to 30 nm.
  • the zeta potential of the suspension is about 65 mV.
  • the LiMn 2 O 4 particles contained in the suspension are subsequently deposited on a substrate made of a 100 ⁇ m thick copper foil.
  • the deposit is made by applying between the substrate and a counter electrode, both immersed in the colloidal suspension, a voltage of 100 V until a deposit of 4 .mu.m thick.
  • This deposit is then compacted under a pressure of 500 MPa, dried for 1 hour at 90 ° C before being densified by a heat treatment of 500 ° C, carried out for 1 hour.
  • the deposit thus obtained has a porosity of less than 10%.
  • Example 2 Suspension of cathode particles and deposition of a cathode
  • Nanometric powders of LiMn 1.5 Ni 0.4 Cr 0.1 O 4 were synthesized as described in Example 5a below. These nanopowders were crushed and dispersed in alcohol in order to obtain a suspension at 20 g / l of LiMn 1.5 Ni 0.4 Cr 0.1 O 4 . The grinding dispersion was conducted until the size of the suspended particles reached 30 nm. This suspension was then diluted in a ketone-based solvent to obtain a suspension of 5 g / l. The deposition conditions were 70 V / cm, which made it possible to obtain a deposit approximately 1 ⁇ m thick after only a few seconds of anaphoresis.
  • a Li 4 Ti 5 O 12 powder consisting of nanometric-sized particles is synthesized according to the method described in the article "Phase-pure nanocrystalline Li4Ti5O12 for a lithium-ion battery" by M. Kalbac et al., J Solid State Elecrtochem (2003) 8: 2-6 .
  • the solution obtained is subsequently hydrolysed with a 4% aqueous solution of polyethylene glycol.
  • the mixture is then mixed for 11 hours before being evaporated at 40 ° C until a viscous paste is obtained. After calcination at 500 ° C., a Li 4 Ti 5 O 12 powder is obtained.
  • This powder is then suspended in ethanol with a concentration of 20 g / l.
  • the suspension is introduced into the bowl of a ball mill previously filled with ceramic balls of diameter 0.1 mm. Grinding for 3 hours in the presence of a few milliliters of polyacrylic acid which serves as a complexing agent, which allows to obtain a colloidal solution having particles whose size (D 50 ) is equal to about 8 nm.
  • the zeta potential of the suspension is equal to 60 mV.
  • the Li 4 Ti 5 O 12 particles contained in the suspension are subsequently deposited on a substrate consisting of a 100 ⁇ m thick copper foil.
  • the deposition is carried out by applying between the substrate and a counter-electrode, both immersed in the colloidal suspension, a voltage of 200 V until a deposit 8 microns thick.
  • This deposit is then compacted under a pressure of 500 MPa, dried for 1 hour at 90 ° C before being densified by a heat treatment at 450 ° C, carried out for 2 hours.
  • the deposit thus obtained has a porosity of less than 10%.
  • the nanoparticles of L 14 Ti 5 O 12 were purchased from Aldrich and then crushed in ethyl alcohol with a concentration of 10 g / l. After this milling-dispersion step, the suspension was sonicated and then decanted. We took only the supernatant from the suspension after decantation to be certain to obtain a monodisperse colloidal suspension of nanoparticles, without agglomerates of sizes greater than 100 nm.
  • a suspension was thus obtained without additions of stabilizer.
  • the stability of nano colloids greatly depends on the size of the particles and their concentrations in the suspension.
  • the particle size is around ten nanometers, they can be stable in suspensions without adding stabilizers.
  • the high specific surface area of these particles and their low mass leads to the balance of the interactions leading to the system behaving like a real gas that can condense, giving rise to a colloidal crystal.
  • the electrophoretic deposits of these nanoparticles allow us to condense on the surface of the substrate this so-called colloidal crystal phase.
  • the Li 4 Ti 5 O 12 electrode was deposited in a thin layer by electrophoresis of the nanoparticles on an electro polished aluminum strip.
  • the deposition conditions used were 10 V / cm, which made it possible to obtain a compact deposition approximately 0.5 ⁇ m thick after only thirty seconds of anaphoresis.
  • the deposit was then annealed at 500 ° C for 1 hour and then pressed at 50 MPa.
  • Li 2 CO 3 powder A small amount of Li 2 CO 3 powder is dissolved in a mixture of citric acid and ethylene glycol heated to 70 ° C. CO 2 evolution is observed at each added portion.
  • the temperature of the mixture is raised to 90 ° C., and Mn (NO 3 ) 2 .4H 2 O, Ni (NO 3 ) 2 .6H 2 O and Cr (NO 3 ) 2 are then added in stoichiometric amounts.
  • 9H 2 O to the latter solution and the temperature of the mixture is increased to 140 ° C until a hard mass bubbled.
  • the latter is then passed to the oven at 250 ° C until a powder.
  • the powder obtained is finally calcined at 800 ° C. for 6 hours.
  • the resulting powder can be used to prepare cathode films in Li-ion type batteries.
  • a powder of Li 3 PO 4 and a powder MnSO 4 .4H 2 O are ground in a mortar in a stoichiometric quantity.
  • the ground powder obtained is placed in an autoclave at 190 ° C. for 12 hours.
  • the product obtained is washed, centrifuged and then dried at 40 ° C. overnight.
  • the resulting powder can be used to prepare cathode films in Li-ion type batteries.
  • a Li 3 PO 4 powder and a FeSO 4 .7H 2 O powder are ground in a mortar in a stoichiometric quantity.
  • the ground powder obtained is placed in an autoclave at 190 ° C. for 12 hours.
  • the product obtained is washed, centrifuged and then dried at 40 ° C. overnight.
  • the resulting powder can be used to prepare cathode films in Li-ion type batteries.
  • a nanopowder of Li 3 PO 4 untreated heat-treated at high temperature is placed in an alumina nacelle placed in a tubular furnace.
  • the powder is then heat-treated at 650 ° C. for 2 hours under an ammonia atmosphere.
  • the powder thus obtained can be used to prepare electrolyte films in Li-ion type batteries.
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US20150104713A1 (en) 2015-04-16
KR20140096335A (ko) 2014-08-05
ES2634681T3 (es) 2017-09-28
FR2982084B1 (fr) 2013-11-22
CN104011905B (zh) 2018-01-05
US20180108904A1 (en) 2018-04-19
SI2774194T1 (sl) 2017-08-31
KR20200001620A (ko) 2020-01-06
JP2018073840A (ja) 2018-05-10
KR20190022901A (ko) 2019-03-06
KR102020272B1 (ko) 2019-09-10
CN104011905A (zh) 2014-08-27
JP2014534590A (ja) 2014-12-18
EP2774194A1 (fr) 2014-09-10
KR102081745B1 (ko) 2020-02-26
FR2982084A1 (fr) 2013-05-03

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